WO2013118230A1 - Dispositif de stockage d'énergie et procédé de production d'un polymère et d'une batterie rechargeable non aqueuse - Google Patents

Dispositif de stockage d'énergie et procédé de production d'un polymère et d'une batterie rechargeable non aqueuse Download PDF

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WO2013118230A1
WO2013118230A1 PCT/JP2012/008398 JP2012008398W WO2013118230A1 WO 2013118230 A1 WO2013118230 A1 WO 2013118230A1 JP 2012008398 W JP2012008398 W JP 2012008398W WO 2013118230 A1 WO2013118230 A1 WO 2013118230A1
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polymer
group
storage device
ring structure
power storage
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PCT/JP2012/008398
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English (en)
Japanese (ja)
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雄一 平川
三好　学
英明 篠田
賢佑 四本
晃子 島
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株式会社豊田自動織機
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Priority to JP2013557259A priority Critical patent/JP5811195B2/ja
Publication of WO2013118230A1 publication Critical patent/WO2013118230A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a power storage device such as a secondary battery, an electric double layer capacitor, a lithium ion capacitor, and a non-aqueous secondary battery, and a method for producing a polymer suitable as a binder used for these electrodes.
  • a lithium ion secondary battery is a secondary battery having a high charge / discharge capacity and capable of high output. Currently, it is mainly used as a power source for portable electronic devices, and further expected as a power source for electric vehicles that are expected to be widely used in the future.
  • a lithium ion secondary battery has an active material capable of inserting and removing lithium (Li) in a positive electrode and a negative electrode, respectively. And it operates by moving lithium ions in the electrolyte provided between the two electrodes.
  • lithium-containing metal composite oxides such as lithium cobalt composite oxide are mainly used as the active material for the positive electrode, and carbon materials having a multilayer structure are mainly used as the active material for the negative electrode. Yes.
  • the performance of the lithium ion secondary battery depends on the materials of the positive electrode, the negative electrode and the electrolyte constituting the secondary battery.
  • active material that forms an active material is being actively conducted.
  • silicon or silicon oxide having a higher capacity than carbon has been studied as a negative electrode active material.
  • silicon As the negative electrode active material, a battery having a higher capacity than that using a carbon material can be obtained.
  • silicon has a large volume change due to insertion and extraction of lithium during charging and discharging. Therefore, there is a problem that silicon is pulverized and falls off or peels from the current collector, and the charge / discharge cycle life of the battery is short. Therefore, by using silicon oxide as the negative electrode active material, volume change associated with insertion and extraction of Li during charge and discharge can be suppressed more than silicon.
  • SiO x silicon oxide
  • SiO x decomposes into Si and SiO 2 when heat-treated. This is called disproportionation reaction and is separated into two phases of Si phase and SiO 2 phase by solid internal reaction. The Si phase obtained by separation is very fine. Further, the SiO 2 phase covering the Si phase has a function of suppressing the decomposition of the electrolytic solution. Therefore, the secondary battery using the negative electrode active material made of SiO x decomposed into Si and SiO 2 has excellent cycle characteristics.
  • the negative electrode containing the negative electrode active material described above is produced, for example, by applying a slurry containing a negative electrode active material and a binder to a current collector and drying. For this reason, the performance of the binder responsible for the binding between the active material particles and the binding between the active material and the current collector greatly affects the performance of the negative electrode. When the binding force of the binder is low, the adhesiveness between the active material particles and the adhesiveness between the active material and the current collector are lowered, and the current collecting property is lowered.
  • Patent Document 1 describes a negative electrode for a lithium ion secondary battery that contains a polymer selected from the group consisting of polyacrylic acid and polymethacrylic acid, and the polymer contains an acid anhydride group.
  • Patent Document 2 describes that a polymer obtained by copolymerizing acrylic acid and methacrylic acid is used as a negative electrode binder or a positive electrode binder.
  • Patent Document 3 describes that a polymer obtained by copolymerizing acrylamide, acrylic acid and itaconic acid is used as a negative electrode binder or a positive electrode binder.
  • Conventionally used negative electrode binders include fluorine-containing polymers such as polyvinylidene fluoride (PVdF), water-soluble cellulose derivatives such as carboxymethyl cellulose (CMC), and water-soluble polymers such as polyacrylic acid.
  • PVdF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • polyacrylic acid water-soluble polymers
  • the present invention has been made in view of the above circumstances, and its main object is to provide a power storage device and a non-aqueous secondary battery that have excellent followability to volume changes during use and improved load characteristics. There is.
  • a feature of the power storage device of the present invention that solves the above problems is a power storage device having an electrode including a binder, the binder having a core portion and an arm portion made of a polymer chain extending from the core portion, and the core portion Has a ring structure of a four-membered ring or more, the arm part is composed of a polymer of an acid monomer having a carboxyl group, the arm part extends from three or more carbon atoms constituting the ring structure of the core part, One end of the arm part contains a polymer bonded to a carbon atom constituting the ring structure of the core part through a single bond or an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. It is in.
  • the number of arm portions is 3, and a structure extending from 3 carbon atoms constituting the ring structure of the core portion can be obtained.
  • this polymer is referred to as a first polymer.
  • the arm portion may have a structure extending from all the carbon atoms constituting the ring structure of the core portion.
  • this polymer is referred to as a second polymer.
  • this polymer can be a polymer containing a transition metal ion that forms a polymer complex with the carboxyl group of the arm part.
  • this polymer is referred to as a third polymer.
  • the arm part may be a polymer comprising a polymer of an acid monomer having a carboxyl group and a styrene polymer, and the styrene polymer is contained in at least a part of at least one arm part.
  • this polymer is referred to as a fourth polymer.
  • nonaqueous secondary battery of the present invention is characterized by a nonaqueous secondary battery having an electrode having an active material layer, wherein the active material layer includes the binder according to the present invention.
  • the polymer production method of the present invention is characterized in that it has a core part and an arm part composed of a polymer chain extending from the core part, the core part has a ring structure of four or more members, and the arm part is a carboxyl group.
  • the arm part extends from all the carbon atoms constituting the ring structure of the core part, and one end of each arm part is a single bond or a carbon atom constituting the ring structure of the core part.
  • a matrix compound comprising a conjugated monomer having no t-butyl group and capable of generating radicals, and a ring structure having four or more rings and a halogen group bonded to all of the carbon atoms constituting the ring structure via an alkyl group;
  • the total reaction point of the parent skeleton compound refers to all the reaction points of the parent skeleton compound.
  • the number of moles of the total reaction point of the base skeleton compound refers to the number of moles obtained by multiplying the number of reaction points, which is the point at which a halogen group can be bonded in the core part, by the number of moles of the core part itself.
  • the binder containing the polymer described above is included in the electrode, rigidity is expressed by the core portion having a ring structure, and adhesiveness and flexibility are provided by the arm portion having many carboxyl groups. Expressed. Therefore, the load characteristics of the power storage device of the present invention are improved.
  • the power storage device is a lithium ion secondary battery
  • a phenomenon such as proton hopping conduction by the Grothus mechanism occurs, and lithium ions hop through the carboxyl group of the arm part and easily move. For this reason, a high discharge capacity and high conductivity are exhibited.
  • the conductivity is improved by the transition metal ions contained in the polymer complex, an increase in resistance in the electrode can be suppressed when used as a binder for an electrode of a power storage device. .
  • the first to third polymers are soluble in water but not in N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • a slurry composed of a negative electrode active material, a conductive additive, a binder, and an organic solvent such as N-methyl-2-pyrrolidone (NMP) is used. If the polymer is used as a binder, water must be used as a solvent, and there is a problem that the types of conductive assistants and negative electrode active materials are limited.
  • the compatibility with the organic solvent is improved by the polymer of styrene contained in the arm portion, so that it becomes soluble in N-methyl-2-pyrrolidone (NMP) and the like, and is a non-aqueous secondary battery. It can use for this electrode.
  • NMP N-methyl-2-pyrrolidone
  • the arm portion can be grown from all the carbon atoms constituting the ring structure without using a conjugated monomer having a t-butyl group.
  • the reaction stopping step can be performed without using formic acid, and safety is high. That is, by using a metal halide in an amount that gives a molar ratio of 0.8 or less when the number of moles of the total reaction point of the base skeleton compound is 1, the reaction rate in the polymerization step can be reduced, so that the carbon atoms constituting the ring structure It becomes easier to grow the arm part from all of the above. Further, by performing the water addition step at an appropriate time, the reaction time in the polymerization step is increased while the arm portion is grown from all the carbon atoms constituting the ring structure, so that the reaction time can be shortened.
  • FIG. 1 shows a structural formula of a star polymer synthesized in one example of the present invention.
  • 3 is a graph showing discharge capacities of lithium ion secondary batteries according to Example 1 and Comparative Example 1.
  • 4 is a graph showing discharge IR drops of lithium ion secondary batteries according to Example 1 and Comparative Example 1.
  • 6 is a graph showing discharge capacity retention rates of lithium ion secondary batteries according to Example 1 and Comparative Example 1.
  • the structural formula of the star polymer synthesized in the second embodiment of the present invention is shown.
  • 6 is a graph showing discharge capacities of lithium ion secondary batteries according to Example 2 and Comparative Example 2.
  • 3 shows a structural formula of a star polymer synthesized in a third embodiment of the present invention.
  • the polymer used for the binder of the power storage device of the present invention includes a core part and an arm part.
  • the core portion includes a ring structure having four or more members, and may be derived from a monocyclic compound composed only of carbon, or derived from a heterocyclic compound including an element other than carbon. It may be.
  • Examples of the four-membered monocyclic compound include cyclobutane, cyclobutene, and cyclobutadiene
  • examples of the four-membered heterocyclic compound include azetidine, oxetane, azeto, and trimethylene sulfide.
  • the ring structure of a four-membered ring needs to have at least three carbon atoms forming the ring structure.
  • Cyclopentane is a typical example of a five-membered monocyclic compound
  • examples of a five-membered heterocyclic compound include azolidine, azole, imidazole, pyrazole, imidazoline, pyrrole, which contain nitrogen as a hetero atom.
  • examples include oxolane and oxygen containing oxygen as a hetero atom, thiol containing nitrogen as a hetero atom, oxazole containing nitrogen and oxygen as a hetero atom, and thiazole containing nitrogen and sulfur as a hetero atom.
  • a five-membered ring structure requires at least three carbon atoms.
  • Examples of the six-membered monocyclic compound include benzene and cyclohexane
  • the six-membered heterocyclic compound includes piperidine containing nitrogen as a hetero atom, pyridine, pyrazine, tetrahydropyran containing oxygen as a hetero atom
  • Examples include thiane and thiapyran containing sulfur as a hetero atom, morpholine containing nitrogen and oxygen as a hetero atom, and thiazine containing nitrogen and sulfur as a hetero atom.
  • a six-membered ring structure requires at least three carbon atoms.
  • Examples of the seven-membered monocyclic compounds include cycloheptane and cycloheptene.
  • Examples of the seven-membered heterocyclic compounds include hexamethyleneimine (azeban), azatropylidene (azepine), heterozygote containing nitrogen as a hetero atom.
  • Examples include hexamethylene oxide (oxeban) containing oxygen as an atom, oxycycloheptatriene (oxepin), and tiotropylidene (thiepin) containing sulfur as a heteroatom.
  • a seven-membered ring structure must have at least three carbon atoms.
  • Examples of the eight-membered monocyclic compound include cyclooctane and cyclooctene. It may be a core portion derived from a monocyclic compound having at least eight members or a heterocyclic compound.
  • the ring structure of an eight-membered ring needs to have at least 3 carbon atoms.
  • the core part may be a single ring or may have a polycyclic structure composed of a plurality of rings.
  • a polycyclic structure composed of a plurality of rings.
  • the arm part is a polymer chain extending from the core part, and is made of a polymer of an acid monomer having a carboxyl group.
  • the acid monomer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid and (anhydrous) maleic acid.
  • the arm part may be a homopolymer of one kind of monomer selected from these acid monomers, or may be a copolymer of a plurality of monomers.
  • polyacrylic acid polymethacrylic acid, polymaleic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic acid copolymer, methacrylic acid-maleic acid copolymer, acrylic acid-fumaric acid copolymer, methacrylic acid -Fumaric acid copolymer, acrylic acid-itaconic acid copolymer, methacrylic acid-itaconic acid copolymer, acrylic acid-methacrylic acid-maleic acid copolymer, acrylic acid-methacrylic acid-fumaric acid copolymer, acrylic Examples thereof include an acid-methacrylic acid-itaconic acid copolymer.
  • a copolymer obtained by copolymerizing a part of the acid monomer in place of another monomer such as styrene, a styrene derivative, butylene, isobutylene, an acrylic ester, a methacrylic ester, or acrylonitrile may be used.
  • the arm part extends from three or more carbon atoms constituting the ring structure of the core part.
  • the arm part in the first polymer extends from three carbon atoms constituting the ring structure.
  • the arm part in a 2nd polymer is each extended from all the carbon atoms which comprise the ring structure of a core part.
  • each arm part is bonded to a carbon atom constituting the ring structure of the core part through a single bond, an ether group, an ester group, a carbonyl group, an alkylene group or a divalent group obtained by combining these.
  • the polymers constituting each arm part may be the same or different.
  • At least one arm part includes a polyacrylic acid skeleton represented by Formula 1.
  • a polyacrylic acid skeleton represented by Formula 1.
  • the molecular weight of the polymer constituting at least one arm part is preferably in the range of 1,000 to 200,000, more preferably 1,000 to 100,000, 1,000 to 50,000, and 1,000 to 10,000, respectively, in number average molecular weight (Mn). If the molecular weight of the arm portion is less than 1,000, flexibility and adhesion are insufficient, and if the molecular weight of the arm portion is larger than 200,000, it is difficult to dissolve in the solvent. When the molecular weight of the arm part is 50,000 to 200,000, there is a possibility of gelation, and when used as a binder, there is network-like adhesion. In addition, when the molecular weight of the arm part is 1,000 to 50,000, the distribution of the chains is stable, and thus the dispersibility is high. The molecular weight of each arm part may be the same or different.
  • carbon atoms that make up the ring structure of the core not only hydrogen but also various substituents such as alkyl groups such as methyl and ethyl groups, carboxyl groups, and hydroxyl groups are bonded to carbon atoms that are not bonded to the arm. You may do it.
  • the transition metal ion that forms a polymer complex with the carboxyl group of the arm portion is selected from the group of copper ion, zinc ion, nickel ion, manganese ion, cobalt ion, iron ion, molybdenum ion, and the like. Can be used. Of these, copper ions, zinc ions, and manganese ions are preferably used.
  • the content of the transition metal ion is determined according to the valence of the transition metal ion and the amount of the carboxyl group in the polymer, and can be included so as to be equivalent to the carboxyl group at the maximum value.
  • the molar amount of the transition metal is preferably in the range of 0.001 to 30%. If the content of transition metal ions is less than this range, the effect of improving the conductivity will not be manifested, and even if transition metal ions are included beyond this range, the effect of improving the conductivity will be saturated and the physical properties such as binding properties will be saturated. Will fall.
  • the arm portion is composed of a polymer of an acid monomer having a carboxyl group and a polymer of styrene.
  • the number of arm portions is 6, some of them can be formed from a polymer of acid monomers having a carboxyl group, and the remaining arm portions can be formed from a styrene polymer.
  • one arm portion may include a polymer block of an acid monomer having a carboxyl group and a polymer block of styrene. From the viewpoint of compatibility with an organic solvent, it is preferable that a polymer block of styrene exists on the terminal side of the arm portion.
  • composition ratio (polymer of styrene / polymer of acid monomer) of the polymer of the acid monomer having a carboxyl group and the polymer of styrene is preferably in the range of 3 to 30 by mass ratio. If the styrene polymer is less than this range, the compatibility with the organic solvent is reduced. If the styrene polymer is more than this range, the binding property as a binder is lowered, and the lithium transport ability is also lowered. Become.
  • a method of polymerizing a monomer using a polyfunctional initiator, a coupling method of a living polymer and a polyfunctional reagent, a divinyl compound that can be polymerized into a living polymer A method of adding an appropriate amount, a homopolymerization method of a macromonomer, and the like can be employed.
  • the number of arm portions can be easily controlled by using a method of polymerizing a monomer using a polyfunctional initiator or a coupling method of a living polymer and a polyfunctional reagent.
  • a method of polymerizing a monomer using a polyfunctional initiator is suitable for the synthesis of a star polymer having a long-chain arm portion.
  • a star polymer may be synthesized using an ester of an acid monomer as an arm portion monomer, and then the ester group may be hydrolyzed to generate a carboxyl group.
  • a base skeleton compound comprising a conjugated monomer having a t-butyl group and capable of generating radicals, and a ring structure having four or more rings and a halogen group bonded to all of the carbon atoms constituting the ring structure via an alkyl group
  • a polymerization process in which an amine catalyst is dissolved in a solvent, and a metal radical that generates active halogen by heating is added and heated to carry out living radical polymerization, and an acid and an alcohol are added to the resulting reaction solution to add an amine system.
  • a precipitation step of neutralizing the catalyst and depositing a precipitate, a filtration step of washing and filtering the precipitate to obtain a polymer precursor by drying, and dissolving the polymer precursor in an organic solvent and adding formic acid to hydrolyze A production method comprising a reaction stopping step and a purification step of washing and drying the aqueous phase of the obtained mixture can be used.
  • an acidic solution prepared by dissolving the transition metal in an inorganic acid such as hydrochloric acid or nitric acid is used as the first polymer or the second polymer, Alternatively, the solvent may be removed after mixing with the fourth polymer.
  • the metal of the metal halide (activator) that generates active halogen by heating can be included as part or all of the transition metal ion. .
  • the above-described polymer can be used alone as a binder for an electrode of a power storage device.
  • epoxy resin, melamine resin, polyblock isocyanate, polyoxazoline, polycarbodiimide and other curing agents, ethylene glycol, glycerin, polyether polyol, polyester polyol, acrylic oligomer, phthalic acid as long as the properties as a binder are not impaired.
  • the above-described production method has a problem that the raw material cost is high because a conjugated monomer having a t-butyl group is used as a raw material.
  • the reaction stopping step it was necessary to use strong acid and highly toxic formic acid.
  • the polymerization process requires a long time of about 13 hours, and the polymerization reaction is required to be shortened. Therefore, according to the production method of the present invention, a star polymer can be produced in a short reaction without using a conjugated monomer having a t-butyl group or formic acid.
  • a polymer is produced by a living radical polymerization method. That is, first, a matrix comprising a conjugated monomer having no t-butyl group and capable of generating radicals, and a halogen group bonded to all of the carbon atoms constituting the ring structure and all the carbon atoms constituting the ring structure via an alkyl group.
  • a polymerization step is performed in which a skeletal compound, an amine-based ligand, and a metal halide that generates an active halogen by heating are dissolved in a solvent and heated to perform living radical polymerization.
  • Conjugated monomers that do not have a t-butyl group and can generate radicals include acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, methacrylic acid, methyl methacrylate, and ethyl methacrylate.
  • Illustrative examples include isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, itaconic acid, itaconic acid ester, fumaric acid, and fumaric ester. Only one of these may be used, or a plurality of types may be mixed and used.
  • the parent skeleton compound is composed of the above-described four or more ring structures and a halogen group bonded to all of the carbon atoms constituting the ring structure via an alkyl group.
  • a host skeleton compound in which a halogen group is bonded to all six carbon atoms constituting the benzene ring via an alkyl group can be used.
  • the alkyl group is not particularly limited, but is preferably up to about a methyl group, an ethyl group or a propyl group having a small carbon number.
  • the halogen group include a bromine group, an iodine group, a chlorine group, and a fluorine group, and a bromine group or a chlorine group is preferable.
  • the amine-based ligand is also called a ligand, and has a function of promoting an initial reaction between the parent skeleton compound and the conjugated monomer.
  • TMEDA N, N, N ', N'-tetramethylethylenediamine
  • bpy (2,2'-bipyridine)
  • NPPMI N-propyl-pyridylmethanimine
  • NOPMI N-octyl-pyridylmethanimine
  • PMDETA N, N, N ', N ”, N” -pentamethyldiethylenetriamine
  • tNtpy HMTETA (1,1,4,7,10,10-hexamethyltriethylenetetramine)
  • TPMA tris (pyridine-2-methyl) amine
  • cyclam B TPEDA (N, N, N ', N',-tetrakis (2-pyridylmethyl)
  • the solvent is not particularly limited as long as it dissolves the base skeleton compound, the conjugated monomer, the amine-based ligand, and the metal halide, and alcohols, aromatic hydrocarbons, esters, ethers, etc. can be used alone. Alternatively, a plurality of types can be mixed and used. In view of the solubility of the complex, the stability of the complex, the chain transferability of the radical, and the reaction rate, 2-propyl alcohol is preferred.
  • the metal halide is added in a molar ratio of 0.8 or less, preferably 0.6 or less and 0.3 or more, where the number of moles of the total reaction point of the base skeleton compound is 1. If the addition amount of the metal halide exceeds this range, the polymerization reaction rate increases, so that it is difficult to grow the arm portion from all the carbon atoms constituting the ring structure. On the other hand, if the addition amount of the metal halide is less than this range, the reaction time becomes too long and the probability of occurrence of a side reaction increases, which is not preferable.
  • the addition amount of the metal halide is desirably 1 or more in terms of a molar ratio where the number of moles of the amine-based ligand is 1.
  • the reaction proceeds more rapidly from the viewpoint of the reaction rate when the molar ratio is 1 or more than when the molar ratio is less than 1.
  • the metal halide deposits halogen from the matrix skeleton compound, carbon radicals are generated in the matrix skeleton compound, and polymerization of the conjugated monomer existing in the system begins.
  • the growing radical is again bonded to the halogen to become a polymer having a C—X bond at the terminal.
  • the halogen atom (X) of the C—X bond is transferred again to the metal halide, and the growth reaction continues, so that the molecular weight increases with time.
  • carbon radicals are generated at all the carbon atoms constituting the ring structure of the parent skeleton compound at the beginning of the reaction, and the polymerization of the conjugated monomer starts almost simultaneously from each carbon radical.
  • carbon radicals can be generated on all the carbon atoms constituting the ring structure of the parent skeleton compound.
  • the amount of water added is 50% or less, desirably 30% or less, based on the solvent used. If the amount added is large, side reactions may occur.
  • the time for carrying out the water addition step is within 8 hours from the start of the reaction, preferably from 1 hour to 4 hours. Further, it is desirable that the water is added after all the reaction points of the parent skeleton compound have reacted. If the addition of water is too early, carbon atoms that are not deposited in the growth reaction may remain among the carbon atoms that constitute the ring structure. In addition, it can be judged by confirming that the peak derived from an unreacted part disappears by NMR whether all the reaction points of the base skeleton compound reacted.
  • acid and alcohol are added to the obtained reaction solution to neutralize the amine-based ligand and precipitate the precipitate.
  • Any acid can be used as long as it can neutralize the amine-based ligand to make the system acidic, and strong acids such as nitric acid and sulfuric acid can be used. However, unreacted conjugated monomers may be reacted. It is desirable to use weak acids such as acetic acid, tartaric acid and oxalic acid.
  • alcohol is added in order to precipitate the produced polymer precursor, and the kind of alcohol is not ask
  • the deposited precipitate is washed, filtered and dried to obtain a polymer precursor.
  • the polymer precursor such as acetone may be dissolved using a soluble organic solvent, reprecipitated by adding methanol or the like, filtered, and this operation may be repeated multiple times. desirable.
  • the resulting polymer precursor has a plurality of arms extending from the carbon atoms constituting the ring structure of the parent skeleton compound and having a homopolymer skeleton of a conjugated monomer, and a halogen group is bonded to the end thereof.
  • the reaction has not stopped yet. Therefore, a reaction stop process is performed. Therefore, in the production method of the present invention, the polymer precursor is dissolved in an organic solvent and an alkali such as KOH, NaOH, or ammonia is added as a reaction stopping step. By doing so, a hydrolysis reaction occurs, the halogen group at the end of the arm part becomes a hydroxyl group, and when an ester group exists in the arm part, the ester group becomes a carboxyl group.
  • a solvent what can melt
  • the mixture after hydrolysis is separated into an organic solvent phase and an aqueous phase by standing, and the polymer is dissolved in the aqueous phase. Accordingly, a purification step is performed in which the aqueous phase is neutralized, washed and then dried.
  • an acid such as acetic acid or nitric acid can be used, and washing can be performed by a dialysis method using pure water. Thereafter, the polymer is obtained by drying using a freeze drying method or the like.
  • a negative electrode of a non-aqueous secondary battery using the polymer as a binder a negative electrode active material powder, a conductive assistant such as carbon powder, the polymer, and an appropriate amount of an organic solvent are added and mixed.
  • the slurry can be produced by applying it onto a current collector by a roll coating method, dip coating method, doctor blade method, spray coating method, curtain coating method, etc., and drying or curing the binder. .
  • the binder is required to bind the active material or the like in as little amount as possible, but the addition amount is preferably 0.5 wt% to 50 wt% of the total of the active material, the conductive auxiliary agent, and the binder.
  • the binder is less than 0.5 wt%, the moldability of the electrode is lowered, and when it exceeds 50 wt%, the energy density of the electrode is lowered.
  • a current collector is a chemically inert electronic high conductor that keeps current flowing through an electrode during discharging or charging.
  • the current collector can adopt a shape such as a foil or a plate, but is not particularly limited as long as it has a shape according to the purpose.
  • a copper foil or an aluminum foil can be suitably used as the current collector.
  • the negative electrode active material known materials such as graphite, hard carbon, silicon, carbon fiber, tin (Sn), and silicon oxide can be used.
  • a silicon oxide represented by SiO x (0.3 ⁇ x ⁇ 1.6) is particularly preferable.
  • Each particle of the silicon oxide powder is composed of SiO x decomposed into fine Si and SiO 2 covering Si by a disproportionation reaction.
  • x is less than the lower limit, the Si ratio increases, so that the volume change during charge / discharge becomes too large, and the cycle characteristics deteriorate.
  • x exceeds the upper limit value the Si ratio is lowered and the energy density is lowered.
  • a range of 0.5 ⁇ x ⁇ 1.5 is preferable, and a range of 0.7 ⁇ x ⁇ 1.2 is more desirable.
  • a raw material silicon oxide powder containing amorphous SiO powder is heat-treated at 800 to 1200 ° C. for 1 to 5 hours in an inert atmosphere such as in a vacuum or in an inert gas.
  • a silicon oxide powder containing two phases of an amorphous SiO 2 phase and a crystalline Si phase is obtained.
  • the silicon oxide a composite of 1 to 50% by mass of a carbon material with respect to SiO x can be used.
  • cycle characteristics are improved.
  • the composite amount of the carbon material is less than 1% by mass, the effect of improving the conductivity cannot be obtained, and when it exceeds 50% by mass, the proportion of SiO x is relatively decreased and the negative electrode capacity is decreased.
  • the composite amount of the carbon material is preferably in the range of 5 to 30% by mass with respect to SiO x , and more preferably in the range of 5 to 20% by mass.
  • a CVD method or the like can be used.
  • the silicon oxide powder preferably has an average particle size in the range of 1 ⁇ m to 10 ⁇ m.
  • the average particle size is larger than 10 ⁇ m, the charge / discharge characteristics of the non-aqueous secondary battery are degraded.
  • the average particle size is less than 1 ⁇ m, the particles are aggregated and become coarse particles. May decrease.
  • Conductive aid is added to increase the conductivity of the electrode.
  • Carbon black, graphite, acetylene black (AB), ketjen black (KB), vapor grown carbon fiber (Vapor Grown Carbon Fiber: VGCF), etc. are used alone or in combination of two or more as conductive aids.
  • the amount of the conductive auxiliary agent used is not particularly limited, but can be, for example, about 20 to 100 parts by mass with respect to 100 parts by mass of the active material. If the amount of the conductive auxiliary is less than 20 parts by mass, an efficient conductive path cannot be formed, and if it exceeds 100 parts by mass, the moldability of the electrode deteriorates and the energy density decreases. Note that when the silicon oxide combined with the carbon material is used as the active material, the amount of the conductive auxiliary agent added can be reduced or eliminated.
  • organic solvent there is no particular limitation on the organic solvent, and a mixture of a plurality of solvents may be used.
  • N-methyl-2-pyrrolidone and N-methyl-2-pyrrolidone and ester solvents ethyl acetate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, etc.
  • glyme solvents diglyme, triglyme, tetraglyme, etc.
  • the mixed solvent is particularly preferable.
  • the silicon oxide constituting the negative electrode may be predoped with lithium.
  • an electrode formation method in which a half battery is assembled using metallic lithium as the counter electrode and electrochemically doped with lithium can be used.
  • the amount of lithium doped is not particularly limited.
  • the positive electrode may be anything that can be used in a non-aqueous secondary battery.
  • the positive electrode has a current collector and a positive electrode active material layer bound on the current collector.
  • the positive electrode active material layer includes a positive electrode active material and a binder, and may further include a conductive additive.
  • the positive electrode active material, the conductive additive, and the binder are not particularly limited as long as they can be used in the nonaqueous secondary battery.
  • the positive electrode active material examples include lithium metal, LiCoO 2 , Li [Mn 1/3 Ni 1/3 Co 1/3 ] O 2 , Li 2 MnO 3 , and sulfur.
  • the current collector may be any material that is generally used for a positive electrode of a lithium ion secondary battery, such as aluminum, nickel, and stainless steel.
  • the conductive auxiliary agent the same ones as described in the above negative electrode can be used.
  • the electrolytic solution is obtained by dissolving a lithium metal salt as an electrolyte in an organic solvent.
  • the electrolytic solution is not particularly limited.
  • an aprotic organic solvent such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or the like should be used.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • a lithium metal salt soluble in an organic solvent such as LiPF 6 , LiBF 4 , LiAsF 6 , LiI, LiClO 4 , LiCF 3 SO 3 can be used.
  • an organic solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, or dimethyl carbonate is mixed with a lithium metal salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 at a concentration of about 0.5 mol / l to 1.7 mol / l.
  • a lithium metal salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 at a concentration of about 0.5 mol / l to 1.7 mol / l.
  • a dissolved solution can be used.
  • the separator is not particularly limited as long as it can be used for a non-aqueous secondary battery.
  • the separator separates the positive electrode and the negative electrode and holds the electrolytic solution, and a thin microporous film such as polyethylene or polypropylene can be used.
  • the shape is not particularly limited, and various shapes such as a cylindrical shape, a stacked shape, and a coin shape can be employed. Regardless of the shape, a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body, and the space between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal is used for current collection. After connecting using a lead or the like, the electrode body is sealed in a battery case together with an electrolytic solution to form a battery.
  • Figure 1 shows the polymer used in the electricity storage device of this example.
  • This star polymer is composed of a core part 1 composed of a benzene ring and five arm parts 2 bonded to five of the six carbon atoms constituting the ring structure of the core part 1.
  • Each arm portion 2 has a polyacrylic acid skeleton and is bonded to a carbon atom constituting a benzene ring via a methylene group.
  • a hydroxyl group 3 is bonded to one carbon atom to which the arm portion 2 is not bonded via a methylene group.
  • a hydroxyl group 3 is also bonded to the end of the arm part 2.
  • methyl acrylate was vacuum distilled at room temperature to remove the contained polymerization inhibitor. 20.0 ml of this methyl acrylate, 0.225 g of hexakis (bromomethyl) benzene as a base skeleton compound shown in the chemical formula 2, 5.00 ml of 2-propanol, and tris 2-dimethylaminoethylamine as an amine-based ligand (ligand) 0.57 g was placed in an eggplant-shaped flask, stirred well, and then allowed to stand. Further, 0.182 g of 99.9% pure copper (I) bromide was added as a metal halide (activator), and after deaeration with a vacuum pump, the mixture was sealed.
  • I copper
  • the solution in the flask was heated to 50 ° C. to 52 ° C. while stirring, and after confirming that the solution turned green, the solution was further stirred for 8 hours.
  • copper bromide (I) deposits bromine from the base skeleton compound, and a carbon radical is generated in the base skeleton compound, and polymerization of methyl acrylate existing in the system starts.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution turned initially purplish gray and a trace amount of precipitate formed.
  • the solution was cooled to room temperature, the system was opened, 1.0 ml of acetic acid was added to neutralize the amine ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6-8 volume methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • this polymer precursor is considered to be a star polymer having the structure shown in Chemical Formula 3, the arm portion is polymethyl acrylate, and the tip of the arm portion is a -C-Br group.
  • the polymer precursor was analyzed by 1H-NMR (JOEL® GSX, 400 MHz, deuterated chloroform, 19.7 ° C.).
  • —C—Br group is bonded to the core, the peak appears in the vicinity of 4.56 ppm (reference value).
  • the peak of the —C—Br group bonded to the end of the arm portion appears at a position slightly lower than 4.56 ppm. Therefore, the number of arm portions can be calculated from the area ratio of these two peaks.
  • the resulting polymer is a star polymer with the structure shown in FIG. 1, in which the ester group of the arm part is hydrolyzed to form a carboxyl group, so that the arm part becomes a polyacrylic acid skeleton and a hydroxyl group is bonded to the tip of the arm part. It is.
  • SiO powder manufactured by Sigma-Aldrich Japan, average particle size 5 ⁇ m
  • SiO x powder having an average particle size of 5 ⁇ m.
  • silicon monoxide SiO is a homogeneous solid having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction.
  • the Si phase obtained by separation is very fine.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly and closely joined by a roll press. This was vacuum-dried at 100 ° C. for 3 hours to form a negative electrode having a negative electrode active material layer thickness of 16 ⁇ m.
  • ⁇ Adhesion test> A grid adhesion test (JIS K5400-8.5) was performed in which 100 grids were cut into the negative electrode active material layer at intervals of 1 mm using a cutter knife, and cellophane tape was applied and peeled off. As a result, no peeling of the negative electrode active material layer was observed at all 100 masses, and the star polymer of this example was excellent in adhesion to copper foil, and was a binder of SiO x powder, natural graphite powder, and ketjen black. Excellent in properties.
  • This slurry was applied to a current collector, and a positive electrode mixture layer was laminated on the current collector. Specifically, this slurry was applied to the surface of an aluminum foil (current collector) having a thickness of 20 ⁇ m using a doctor blade.
  • the electrode density was adjusted with a roll press. This was heat-cured at 120 ° C. for 6 hours in a vacuum drying furnace to obtain a positive electrode in which a positive electrode mixture layer having a thickness of about 50 ⁇ m was laminated on the upper layer of the current collector.
  • the positive electrode was cut into 30 mm ⁇ 25 mm and the negative electrode was cut into 31 mm ⁇ 26 mm, and accommodated with a laminate film.
  • a rectangular sheet (40 mm ⁇ 40 mm square, thickness 30 ⁇ m) made of polypropylene resin as a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed. Then, the following electrolytic solution was injected into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • the positive electrode and the negative electrode were provided with a tab that could be electrically connected to the outside, and a part of this tab extended to the outside of the laminate cell. Through the above steps, a lithium ion secondary battery of a single-layer laminate cell was obtained.
  • Example 1 A polymer solution was prepared in the same manner as in Example 1 except that polyacrylic acid (“H-AS” manufactured by Nippon Shokubai Co., Ltd.) was used as the negative electrode binder.
  • the polymer in the polymer solution was a homopolymer of 100 mol% acrylic acid, and its mass average molecular weight measured by GPC was 700,000.
  • a negative electrode for a lithium ion secondary battery was produced in the same manner as in Example 1, and a lithium ion secondary battery was produced in the same manner as in the example.
  • FIG. 2 shows that the lithium ion secondary battery of Example 1 has a higher discharge capacity than that of Comparative Example 1. From FIG. 3, it is clear that the discharge IR drop of the lithium ion secondary battery of Example 1 is greatly reduced and the conductivity is greatly improved as compared with Comparative Example 1. The reason for this is that a phenomenon such as proton hopping conduction by the Grothus mechanism has occurred, and it is assumed that lithium ions hopped through the carboxyl group of the arm portion and moved easily.
  • the discharge capacity maintenance ratio is a value obtained by dividing the discharge capacity at the Nth cycle by the initial discharge capacity ((discharge capacity at the Nth cycle) / (discharge capacity at the first cycle) ⁇ 100).
  • the lithium ion secondary battery of Example 1 has a higher discharge capacity retention rate and improved load characteristics than Comparative Example 1. This is presumably because the negative electrode internal resistance was reduced by about 10% and the strength of the negative electrode was increased by using the first polymer according to the present invention as a binder.
  • FIG. 5 shows the polymer (first polymer) used in the power storage device of this example.
  • This star polymer comprises a core part 1 composed of a benzene ring and three arm parts 2 bonded to three of the six carbon atoms constituting the ring structure.
  • Each arm part 2 has a polyacrylic acid skeleton and is bonded to a carbon atom constituting the ring structure via a methylene group.
  • a methyl group 4 is bonded to three carbon atoms to which the arm part 2 is not bonded.
  • a hydroxyl group 3 is bonded to the end of the arm part 2.
  • methyl acrylate was vacuum distilled at room temperature to remove the contained polymerization inhibitor. 20.0 ml of this methyl acrylate, 1,4,5-tris (bromomethyl) -2,4,6-trimethylbenzene 0.1412 g as a base skeleton compound shown in the chemical formula 5, 7 ml of 2-propanol, 0.57 ml of tris 2-diethylaminoethylamine as a ligand (ligand) was placed in an eggplant-shaped flask, stirred well, and then allowed to stand.
  • copper bromide (I) having a purity of 99.9% as a metal halide (activator) was added in a mass ratio of 3.5 times the mass of the base skeleton compound, and after deaeration with a vacuum pump, it was sealed.
  • the solution in the flask was heated to 50 ° C. to 52 ° C. while stirring, and after confirming that the solution turned green, the solution was further heated and stirred for 13.5 hours.
  • copper bromide (I) deposits bromine from the base skeleton compound, and a carbon radical is generated in the base skeleton compound, and polymerization of methyl acrylate existing in the system starts.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution turned initially purplish gray and a trace amount of precipitate formed.
  • the solution was cooled to room temperature, the system was opened, 1.0 ml of acetic acid was added to neutralize the ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6-8 volume methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • the polymer precursor was analyzed by 1H-NMR (JOEL® GSX, 400 MHz, deuterated chloroform, 19.7 ° C.).
  • the arm portion of this polymer precursor is a polymethyl acrylate skeleton, and bromine is bonded to the tip of the arm portion.
  • This star polymer had a number average molecular weight (Mn) of 23,800 and a weight average molecular weight (Mw) of 24,100 in terms of polystyrene, and the arm portions each had a number average molecular weight (Mn) of 6,300.
  • the ester group of the arm part is hydrolyzed to become a carboxyl group, so that the arm part becomes a polyacrylic acid skeleton, and a hydroxyl group is bonded to the tip of the arm part. It is a polymer.
  • SiO powder manufactured by Sigma-Aldrich Japan, average particle size 5 ⁇ m
  • SiO x powder having an average particle size of 5 ⁇ m.
  • silicon monoxide SiO is a homogeneous solid having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction.
  • the Si phase obtained by separation is very fine.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly and closely joined by a roll press. This was vacuum-dried at 100 ° C. for 3 hours to form a negative electrode having a negative electrode active material layer thickness of 16 ⁇ m.
  • ⁇ Adhesion test> A grid adhesion test (JIS K5400-8.5) was performed in which 100 grids were cut into the negative electrode active material layer at intervals of 1 mm using a cutter knife, and cellophane tape was applied and peeled off. As a result, no peeling of the negative electrode active material layer was observed at all 100 masses, and the star polymer of this example was excellent in adhesion to copper foil, and was a binder of SiO x powder, natural graphite powder, and ketjen black. Excellent in properties.
  • a positive electrode active material Li [Mn 1/3 Ni 1/3 Co 1/3 ] O 2 As a positive electrode active material Li [Mn 1/3 Ni 1/3 Co 1/3 ] O 2 , acetylene black (AB) as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder resin are mixed to form a slurry-like positive electrode A composite was prepared.
  • This slurry was applied to a current collector, and a positive electrode mixture layer was laminated on the current collector. Specifically, this slurry was applied to the surface of an aluminum foil (current collector) having a thickness of 20 ⁇ m using a doctor blade.
  • the electrode density was adjusted with a roll press. This was heat-cured at 120 ° C. for 6 hours in a vacuum drying furnace to obtain a positive electrode in which a positive electrode mixture layer having a thickness of about 50 ⁇ m was laminated on the upper layer of the current collector.
  • the positive electrode was cut into 30 mm ⁇ 25 mm and the negative electrode was cut into 31 mm ⁇ 26 mm, and accommodated with a laminate film.
  • a rectangular sheet (40 mm ⁇ 40 mm square, thickness 30 ⁇ m) made of polypropylene resin as a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed. Then, the following electrolytic solution was injected into the laminated film in a bag shape. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • the positive electrode and the negative electrode were provided with a tab that could be electrically connected to the outside, and a part of this tab extended to the outside of the laminate cell. Through the above steps, a lithium ion secondary battery of a single-layer laminate cell was obtained.
  • Example 2 A polymer solution was prepared in the same manner as in Example 2 except that polyacrylic acid (“H-AS” manufactured by Nippon Shokubai Co., Ltd.) was used as the negative electrode binder.
  • the polymer in the polymer solution was a homopolymer of 100 mol% acrylic acid, and its mass average molecular weight measured by GPC was 700,000.
  • Example 2 Using this polymer solution, a negative electrode for a lithium ion secondary battery was produced in the same manner as in Example 2, and a lithium ion secondary battery was produced in the same manner as in Example 2.
  • the lithium ion secondary battery of Example 2 has a higher 0.2C discharge capacity than Comparative Example 2. This is presumably because the negative electrode internal resistance was reduced by about 10% and the strength of the negative electrode was increased by using the star polymer of the present invention as a binder.
  • FIG. 7 shows the polymer (second polymer) used in the power storage device of this example.
  • This star polymer is composed of a core part 1 composed of a benzene ring and six arm parts 2 bonded to all six carbon atoms constituting the ring structure of the core part 1.
  • the arm portion 2 of the star polymer has a polyacrylic acid skeleton and is bonded to carbon atoms constituting the benzene ring via a methylene group.
  • a hydroxyl group 3 is bonded to the end of each arm part 2.
  • t-butyl acrylate was vacuum distilled at room temperature to remove the contained polymerization inhibitor. 20.0 ml of this t-butyl acrylate, 0.225 g of hexakis (bromomethyl) benzene as a base skeleton compound shown in the chemical formula 2, 5.00 ml of 2-propanol, and Tris 2-as an amine-based ligand (ligand) Dimethylaminoethylamine (0.57 g) was placed in an eggplant-shaped flask, stirred well, and then allowed to stand. Further, 0.182 g of 99.9% pure copper (I) bromide was added as a metal halide (activator), and after deaeration with a vacuum pump, the mixture was sealed.
  • I copper
  • the solution in the flask was heated to 50 ° C. to 52 ° C. while stirring, and after confirming that the solution turned green, the solution was further stirred for 8 hours.
  • copper (I) bromide deposits bromine from the parent skeleton compound
  • a carbon radical is generated in the parent skeleton compound
  • polymerization of t-butyl acrylate existing in the system starts.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution turned initially purplish gray and a trace amount of precipitate formed.
  • the solution was cooled to room temperature, the system was opened, 1.0 ml of acetic acid was added to neutralize the amine ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6-8 volume methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • this polymer precursor is a star polymer having the structure shown in Chemical Formula 7, the arm portion is t-butyl polyacrylate, and the tip of the arm portion is a —C—Br group.
  • the polymer precursor was analyzed by 1H-NMR (JOEL® GSX, 400 MHz, deuterated chloroform, 19.7 ° C.).
  • —C—Br group is bonded to the core, the peak appears in the vicinity of 4.56 ppm (reference value).
  • this polymer precursor was composed of carbon atoms constituting the core benzene ring. It is recognized that the arm part is bonded to all.
  • the resulting polymer is a star polymer having a structure shown in FIG. 7 in which the ester group of the arm portion is hydrolyzed to become a carboxyl group, so that the arm portion becomes a polyacrylic acid skeleton, and a hydroxyl group is bonded to the tip of the arm portion. It is.
  • SiO powder manufactured by Sigma-Aldrich Japan, average particle size 5 ⁇ m
  • SiO x powder having an average particle size of 5 ⁇ m.
  • silicon monoxide SiO is a homogeneous solid having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction.
  • the Si phase obtained by separation is very fine.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly and closely joined by a roll press. This was vacuum-dried at 100 ° C. for 3 hours to form a negative electrode having a negative electrode active material layer thickness of 16 ⁇ m.
  • ⁇ Adhesion test> A grid adhesion test (JIS K5400-8.5) was performed in which 100 grids were cut into the negative electrode active material layer at intervals of 1 mm using a cutter knife, and cellophane tape was applied and peeled off. As a result, no peeling of the negative electrode active material layer was observed at all 100 masses, and the star polymer of this example was excellent in adhesion to copper foil, and was a binder of SiO x powder, natural graphite powder, and ketjen black. Excellent in properties.
  • a slurry-like positive electrode mixture was prepared.
  • This slurry was applied to a current collector, and a positive electrode mixture layer was laminated on the current collector. Specifically, this slurry was applied to the surface of an aluminum foil (current collector) having a thickness of 20 ⁇ m using a doctor blade.
  • the electrode density was adjusted with a roll press. This was heat-cured at 120 ° C. for 6 hours in a vacuum drying furnace to obtain a positive electrode in which a positive electrode mixture layer having a thickness of about 50 ⁇ m was laminated on the upper layer of the current collector.
  • the positive electrode was cut into 30 mm ⁇ 25 mm and the negative electrode was cut into 31 mm ⁇ 26 mm, and accommodated with a laminate film.
  • a rectangular sheet (40 mm ⁇ 40 mm square, thickness 30 ⁇ m) made of polypropylene resin as a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed. Then, the following electrolytic solution was injected into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • FEC fluoroethylene carbonate
  • EC ethylene carbonate
  • MEMC methyl ethyl carbonate
  • DMC dimethyl carbonate
  • Example 9 to 9 show that the lithium ion secondary battery of Example 3 has a higher discharge capacity retention rate and improved load characteristics than Example 1. This is presumably because the internal resistance of the negative electrode was reduced by about 10% and the strength of the negative electrode was increased by using the binder according to Example 3. The reason for this is that a phenomenon such as proton hopping conduction by the Grothus mechanism has occurred, and it is assumed that lithium ions hopped through the carboxyl group of the arm portion and moved easily.
  • Example 3 the same star polymer shown in FIG. 7 as in Example 3 is produced by a synthesis method different from Example 3.
  • This star polymer is composed of a core part 1 composed of a benzene ring and six arm parts 2 bonded to all six carbon atoms constituting the ring structure of the core part 1.
  • the arm portion 2 of the star polymer has a polyacrylic acid skeleton and is bonded to carbon atoms constituting the benzene ring via a methylene group.
  • a hydroxyl group 3 is bonded to the end of each arm part 2.
  • methyl acrylate was vacuum distilled at room temperature to remove the contained polymerization inhibitor.
  • 20.0 ml of this methyl acrylate, 0.2 g of hexakis (bromomethyl) benzene as a base skeleton compound shown in Chemical Formula 2, 5.00 ml of 2-propanol, and 0.6 g of tris 2-dimethylaminoethylamine as an amine-based ligand was placed in an eggplant-shaped flask, stirred well, and allowed to stand.
  • 0.2 g of copper bromide (I) having a purity of 95% was added as a metal halide, and after deaeration with a vacuum pump, the mixture was sealed.
  • the solution in the flask was heated to 50 ° C. to 52 ° C. while stirring, and after confirming that the solution turned green, the solution was further stirred for 8 hours.
  • copper bromide (I) deposits bromine from the base skeleton compound, and a carbon radical is generated in the base skeleton compound, and polymerization of methyl acrylate existing in the system starts.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution turned initially purplish gray and a trace amount of precipitate formed. When all the reaction points of the base skeleton compound reacted, 40% of water was added to the reaction system with respect to the amount of 2-propanol used.
  • the solution was cooled to room temperature, the system was opened, 1.0 ml of acetic acid was added to neutralize the amine ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6-8 volume methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • this polymer precursor is a star polymer having the structure shown in Formula 3, the arm portion is polymethyl acrylate, and the tip of the arm portion is a —C—Br group.
  • the polymer precursor was analyzed by 1H-NMR (JOEL® GSX, 400 MHz, deuterated chloroform, 19.7 ° C.).
  • —C—Br group is bonded to the core, the peak appears in the vicinity of 4.56 ppm (reference value).
  • this polymer precursor contained carbon atoms constituting the benzene ring in the core. It is recognized that the arm part is bonded to all.
  • the ester group of the arm part is hydrolyzed to become a carboxyl group, so that the arm part becomes a polyacrylic acid skeleton, and the star of the structure shown in FIG. 7 has a hydroxyl group bonded to the tip of the arm part. It is a polymer.
  • the arm portion can be grown from all the carbon atoms constituting the ring structure without using a conjugated monomer having a t-butyl group.
  • the reaction stopping step can be performed without using formic acid, and safety is high. That is, by using a metal halide in an amount that gives a molar ratio of 0.8 or less when the number of moles of the total reaction point of the base skeleton compound is 1, the reaction rate in the polymerization step can be reduced, so that the carbon atoms constituting the ring structure It becomes easier to grow the arm part from all of the above. Further, by performing the water addition step at an appropriate time, the reaction time in the polymerization step is increased while the arm portion is grown from all the carbon atoms constituting the ring structure, so that the reaction time can be shortened.
  • a polymer precursor was synthesized in the same manner as in Example 4 except that 0.2 g of 99.9% pure copper (I) bromide was added as a metal halide.
  • This polymer precursor was analyzed by 1H-NMR in the same manner as in Example 4.
  • the peak of the —C—Br group bonded to the end of the arm portion appears at a position slightly lower than 4.56 ppm. Therefore, the number of arm portions can be calculated from the area ratio of these two peaks.
  • a polymer precursor represented by the formula 4 was prepared. 6.0 g of the obtained polymer precursor was dissolved in 12.0 ml of toluene, an aqueous potassium hydroxide solution (KOH: 9.5 g, H 2 O: 20 ml) was gradually added, and the solution was allowed to stand at room temperature for 3 days with stirring. . When both the toluene phase and the aqueous phase became transparent when allowed to stand, the reaction was judged to be complete.
  • the aqueous phase was separated and recovered, 10 ml of a 10 mM aqueous copper nitrate solution was added, and then the aqueous nitric acid solution was added to adjust the pH to 3 or less.
  • the obtained acidic aqueous solution was dialyzed with distilled water for 3 days to 1 week using a cellulose tube.
  • the aqueous solution after dialysis was dried by freeze drying to obtain a polymer powder.
  • the ester group of the arm part is hydrolyzed to become a carboxyl group, so the arm part becomes a polyacrylic acid skeleton, and a hydroxyl group is bonded to the tip of the arm part.
  • the star polymer is the same as that of Example 1 except that the structure shown in FIG.
  • Example 6 ⁇ FT-IR analysis>
  • the star polymers prepared in Example 1 and Example 6 were each subjected to FT-IR analysis, and their FT-IR spectra are shown in FIG. From FIG. 11, the star polymer of Example 6 has a specific peak at 1540 cm ⁇ 1, which is identified as a complex formed by COO ⁇ ions and Cu 2+ ions. Therefore, the star polymer of Example 6 contains a copper ion that forms a polymer complex with the carboxyl group of the arm portion.
  • SiO powder manufactured by Sigma-Aldrich Japan, average particle size 5 ⁇ m
  • SiO x powder having an average particle size of 5 ⁇ m.
  • silicon monoxide SiO is a homogeneous solid having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction.
  • the Si phase obtained by separation is very fine.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly and closely joined by a roll press. This was vacuum-dried at 100 ° C. for 3 hours to form negative electrodes each having a negative electrode active material layer thickness of 16 ⁇ m.
  • ⁇ Adhesion test> A grid adhesion test (JIS K5400-8.5) was performed in which 100 grids were cut into the negative electrode active material layer at intervals of 1 mm using a cutter knife, and cellophane tape was applied and peeled off. As a result, no delamination of the negative electrode active material layer was observed at all 100 masses, and the star polymers of Examples 1 and 6 were excellent in adhesion to copper foil, and SiO x powder, natural graphite powder, ketjen Excellent black binding.
  • a slurry-like positive electrode mixture was prepared.
  • This slurry was applied to a current collector, and a positive electrode mixture layer was laminated on the current collector. Specifically, this slurry was applied to the surface of an aluminum foil (current collector) having a thickness of 20 ⁇ m using a doctor blade.
  • the electrode density was adjusted with a roll press. This was heat-cured at 120 ° C. for 6 hours in a vacuum drying furnace to obtain a positive electrode in which a positive electrode mixture layer having a thickness of about 50 ⁇ m was laminated on the upper layer of the current collector.
  • the positive electrode was cut into 30 mm ⁇ 25 mm and the negative electrode was cut into 31 mm ⁇ 26 mm, and accommodated with a laminate film.
  • a rectangular sheet (40 mm ⁇ 40 mm square, thickness 30 ⁇ m) made of polypropylene resin as a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed. Then, the following electrolytic solution was injected into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • EC ethylene carbonate
  • MEC methyl ethyl carbonate
  • DMC dimethyl carbonate
  • the positive electrode and the negative electrode were provided with a tab that could be electrically connected to the outside, and a part of this tab extended to the outside of the laminate cell.
  • FIG. 13 shows a typical structural formula of the polymer (fourth polymer) according to this example.
  • This star polymer is composed of a core part 1 composed of a benzene ring and six arm parts 2 bonded to all six carbon atoms constituting the ring structure of the core part 1.
  • the arm portion 2 of the star polymer has a polyacrylic acid block 20 and a polystyrene block 21, and one end of the polyacrylic acid block 20 is bonded to a carbon atom constituting the core portion 1 through a methylene group.
  • One end of a polystyrene block 21 is bonded to the other end of the polyacrylic acid block 20, and a hydroxyl group 3 is bonded to the other end of the polystyrene block 21.
  • Some cores have a carbon atom to which the arm part 2 is not bonded, and a hydroxyl group 3 is bonded to the carbon atom via a methylene group.
  • methyl acrylate was vacuum distilled at room temperature to remove the contained polymerization inhibitor.
  • 160 ml of this methyl acrylate, 0.5 g of hexakis (bromomethyl) benzene as a base skeleton compound shown in Chemical Formula 2, 20 ml of 2-propanol, and 2 g of tris 2-dimethylaminoethylamine as an amine-based ligand (ligand) was placed in an eggplant-shaped flask, stirred well, and allowed to stand.
  • the reaction atmosphere may be a non-oxidizing atmosphere such as an argon gas atmosphere or a reduced pressure atmosphere as well as a nitrogen gas atmosphere.
  • copper bromide (I) deposits bromine from the base skeleton compound, and a carbon radical is generated in the base skeleton compound, and polymerization of methyl acrylate existing in the system starts.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution turned initially purplish gray and a trace amount of precipitate formed.
  • the solution was cooled to room temperature, the system was opened, 10 ml of acetic acid was added to neutralize the amine ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration of about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • this polymer precursor is a star polymer having the structure shown in Chemical Formula 3, the arm portion is polymethyl acrylate, and the end of the arm portion is a —C—Br group.
  • the polymer precursor was analyzed by 1H-NMR (JOEL® GSX, 400 MHz, deuterated chloroform, 19.7 ° C.).
  • —C—Br group is bonded to the core, the peak appears in the vicinity of 4.56 ppm (reference value).
  • the peak of the —C—Br group bonded to the end of the arm portion appears at a position slightly lower than 4.56 ppm. Therefore, the number of arm portions can be calculated from the area ratio of these two peaks.
  • the average number of arm parts extending from one core part is 5.43, and the number of arm parts extending from one core part is 6, and the star polymer with the structure shown in Formula 3 must be included. I understood.
  • Each arm part had a number average molecular weight (Mn) of 79,900.
  • reaction atmosphere is not limited to a reduced pressure atmosphere, but may be a non-oxidizing atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.
  • copper bromide (I) deposits bromine from the end of the arm part, carbon radicals are generated in the arm part, and polymerization of the styrene monomer present in the system begins.
  • the growing radical is again bonded to bromine and becomes a polymer having a C-Br bond at the terminal.
  • the bromine atom of this C—Br bond moves again to copper (I) bromide, and the growth reaction continues, so the molecular weight increases with time.
  • the solution was cooled to room temperature, the system was opened, 10 ml of acetic acid was added to neutralize the amine ligand, and the mixture was stirred well.
  • the solution in the flask was poured into a 6 to 8-fold volume of methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. At this time, the solution is colored blue by copper ions.
  • the obtained precipitate was collected by filtration, and dissolved in about 5 times the volume of acetone. This solution was poured into a 6-8 volume methanol / acetic acid solution (acetic acid concentration: about 1% by weight) and stirred well to precipitate the polymer precursor. This operation was repeated 3 to 5 times to wash the precipitate, and when the coloring of the methanol / acetic acid solution disappeared, the precipitate of the polymer precursor was collected by filtration and vacuum dried at room temperature.
  • this polymer precursor is a star polymer mainly having a structure represented by the chemical formula (8), the arm portion is composed of a polymethyl acrylate block and a polystyrene block, and the end of the arm portion is a -C-Br group. It has become.
  • the bromine group bonded to the benzene ring via a methylene group also contributes to the reaction, and there is a possibility that a polystyrene block is formed on the benzene ring via the methylene group.
  • the number average molecular weight (Mn) of the polymethyl acrylate block in each arm part was 79,900, and the number average molecular weight (Mn) of the polystyrene block was 22,500.
  • the polystyrene in this polymer precursor determined from NMR was 18.6 mol%.
  • the ester group of the polymethyl acrylate block is hydrolyzed to become a carboxyl group. Therefore, the arm part is composed of a polyacrylic acid block and a polystyrene block, and contains many star polymers having a structure shown in FIG.
  • Example 7 The star polymers of Example 1 and Example 7 were mixed with N-methyl-2-pyrrolidone (NMP) or distilled water so as to have a concentration of 50% by mass, and the solubility was visually determined. The results are shown in Table 1. In addition, what was completely melt
  • NMP N-methyl-2-pyrrolidone
  • the star polymer of Example 7 is excellent in solubility in N-methyl-2-pyrrolidone (NMP), which is caused by including a polystyrene block in the arm portion.
  • NMP N-methyl-2-pyrrolidone
  • SiO powder manufactured by Sigma-Aldrich Japan, average particle size 5 ⁇ m
  • SiO x powder having an average particle size of 5 ⁇ m.
  • silicon monoxide SiO is a homogeneous solid having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction.
  • the Si phase obtained by separation is very fine.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly and closely joined by a roll press. This was vacuum-dried at 100 ° C. for 3 hours to form a negative electrode having a negative electrode active material layer thickness of 16 ⁇ m.
  • ⁇ Adhesion test> A grid adhesion test (JIS K5400-8.5) was performed in which 100 grids were cut into the negative electrode active material layer at intervals of 1 mm using a cutter knife, and cellophane tape was applied and peeled off. As a result, no peeling of the negative electrode active material layer was observed at all 100 masses, and the binder made of the star polymer of Example 7 was excellent in adhesion to the copper foil, and the SiO x powder, natural graphite powder, ketjen black Excellent binding properties.
  • a slurry-like positive electrode mixture was prepared.
  • This slurry was applied to a current collector, and a positive electrode mixture layer was laminated on the current collector. Specifically, this slurry was applied to the surface of an aluminum foil (current collector) having a thickness of 20 ⁇ m using a doctor blade.
  • the electrode density was adjusted with a roll press. This was heat-cured at 120 ° C. for 6 hours in a vacuum drying furnace to obtain a positive electrode in which a positive electrode mixture layer having a thickness of about 50 ⁇ m was laminated on the upper layer of the current collector.
  • the positive electrode was cut into 30 mm ⁇ 25 mm and the negative electrode was cut into 31 mm ⁇ 26 mm, and accommodated with a laminate film.
  • a rectangular sheet (40 mm ⁇ 40 mm square, thickness 30 ⁇ m) made of polypropylene resin as a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed. Then, the following electrolytic solution was injected into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate cell in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • the positive electrode and the negative electrode were provided with a tab that could be electrically connected to the outside, and a part of this tab extended to the outside of the laminate cell.
  • a lithium ion secondary battery of a single-layer laminate cell was obtained. Three lithium ion secondary batteries were made of the same.
  • the power storage device of the present invention can be used for secondary batteries, electric double layer capacitors, lithium ion capacitors, and the like. It is also useful as a non-aqueous secondary battery for motor drive of electric vehicles and hybrid vehicles, personal computers, portable communication devices, home appliances, office equipment, industrial equipment, etc. It can be optimally used for driving motors of electric vehicles and hybrid vehicles. Further, the polymer produced by the production method of the present invention can be used for an electrode binder, a paint, an adhesive, and the like of a power storage device.
  • Core part 2 Arm part 3: Hydroxyl group 4: Methyl group 20: Polyacrylic acid block 21: Polystyrene block

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  • General Chemical & Material Sciences (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne notamment une couche de matériau actif d'électrode, qui est formée en utilisant un liant contenant un polymère comportant : une partie de noyau présentant une structure en anneau à au moins quatre membres ; et des parties de bras qui s'étendent à partir d'au moins trois atomes de carbone constituant une structure en anneau et qui sont formées du polymère d'un monomère acide comprenant un groupe carboxyle. De ce fait, le dispositif de stockage d'énergie de la présente invention présente la capacité d'accompagner des variations de volume au cours de la charge et de la décharge, la caractéristique de charge, le rendement initial et la capacité de charge / décharge du dispositif de stockage d'énergie étant améliorés.
PCT/JP2012/008398 2012-02-06 2012-12-27 Dispositif de stockage d'énergie et procédé de production d'un polymère et d'une batterie rechargeable non aqueuse WO2013118230A1 (fr)

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JP2016066506A (ja) * 2014-09-25 2016-04-28 信越化学工業株式会社 非水電解質二次電池用負極活物質、非水電解質二次電池用負極、及び非水電解質二次電池、並びに負極活物質粒子の製造方法
US10347935B2 (en) 2014-02-03 2019-07-09 Fujifilm Corporation Solid electrolyte composition, electrode sheet for battery and all-solid-state secondary battery in which solid electrolyte composition is used, and method for manufacturing electrode sheet for battery and all-solid-state secondary battery

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US10347935B2 (en) 2014-02-03 2019-07-09 Fujifilm Corporation Solid electrolyte composition, electrode sheet for battery and all-solid-state secondary battery in which solid electrolyte composition is used, and method for manufacturing electrode sheet for battery and all-solid-state secondary battery
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